CN114019068B - Solid phase microextraction device and preparation method thereof - Google Patents
Solid phase microextraction device and preparation method thereof Download PDFInfo
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- CN114019068B CN114019068B CN202111312981.XA CN202111312981A CN114019068B CN 114019068 B CN114019068 B CN 114019068B CN 202111312981 A CN202111312981 A CN 202111312981A CN 114019068 B CN114019068 B CN 114019068B
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- 238000002470 solid-phase micro-extraction Methods 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000002728 pyrethroid Substances 0.000 claims abstract description 29
- 239000000575 pesticide Substances 0.000 claims abstract description 28
- 239000003822 epoxy resin Substances 0.000 claims abstract description 25
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 25
- 238000000576 coating method Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 229920003002 synthetic resin Polymers 0.000 claims abstract description 13
- 239000002952 polymeric resin Substances 0.000 claims abstract description 12
- 239000000835 fiber Substances 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 125000005605 benzo group Chemical group 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- QHQSCKLPDVSEBJ-UHFFFAOYSA-N 1,3,5-tri(4-aminophenyl)benzene Chemical compound C1=CC(N)=CC=C1C1=CC(C=2C=CC(N)=CC=2)=CC(C=2C=CC(N)=CC=2)=C1 QHQSCKLPDVSEBJ-UHFFFAOYSA-N 0.000 claims description 3
- SNLFYGIUTYKKOE-UHFFFAOYSA-N 4-n,4-n-bis(4-aminophenyl)benzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1N(C=1C=CC(N)=CC=1)C1=CC=C(N)C=C1 SNLFYGIUTYKKOE-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 2
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 27
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 21
- 239000012086 standard solution Substances 0.000 description 14
- 239000005946 Cypermethrin Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 229960005424 cypermethrin Drugs 0.000 description 6
- KAATUXNTWXVJKI-UHFFFAOYSA-N cypermethrin Chemical compound CC1(C)C(C=C(Cl)Cl)C1C(=O)OC(C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 KAATUXNTWXVJKI-UHFFFAOYSA-N 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000005892 Deltamethrin Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229960002483 decamethrin Drugs 0.000 description 3
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000012417 linear regression Methods 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VQXSOUPNOZTNAI-UHFFFAOYSA-N Pyrethrin I Natural products CC(=CC1CC1C(=O)OC2CC(=O)C(=C2C)CC=C/C=C)C VQXSOUPNOZTNAI-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 231100000085 chronic toxic effect Toxicity 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 210000000750 endocrine system Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000874 microwave-assisted extraction Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000899 pressurised-fluid extraction Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- HYJYGLGUBUDSLJ-UHFFFAOYSA-N pyrethrin Natural products CCC(=O)OC1CC(=C)C2CC3OC3(C)C2C2OC(=O)C(=C)C12 HYJYGLGUBUDSLJ-UHFFFAOYSA-N 0.000 description 1
- VJFUPGQZSXIULQ-XIGJTORUSA-N pyrethrin II Chemical compound CC1(C)[C@H](/C=C(\C)C(=O)OC)[C@H]1C(=O)O[C@@H]1C(C)=C(C\C=C/C=C)C(=O)C1 VJFUPGQZSXIULQ-XIGJTORUSA-N 0.000 description 1
- 210000004994 reproductive system Anatomy 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000012502 risk assessment Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000194 supercritical-fluid extraction Methods 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 239000012224 working solution Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
- G01N2030/062—Preparation extracting sample from raw material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
- Sampling And Sample Adjustment (AREA)
Abstract
The invention discloses a solid-phase microextraction device and a preparation method thereof, belonging to the crossing field of analytical chemistry and environmental chemistry. The solid-phase microextraction device adopts a novel crystalline porous polymer and epoxy resin composite coating as a functional extraction head, and the solid-phase microextraction efficiency of pyrethroid pesticides is obviously improved by utilizing the synergistic effect of the crystalline porous polymer and the epoxy resin. The extraction efficiency of various commercial SPME extractors can be 1.5-150 times. Thereby remarkably improving the sensitivity of the detection of the pyrethroid substances and well realizing the qualitative and quantitative detection of the pyrethroid pesticides in the water body.
Description
Technical Field
The invention relates to a solid-phase microextractor for SPME-GC/MS, which is used for realizing the detection of pyrethroid pesticides in a water body and belongs to the crossing field of analytical chemistry and environmental chemistry.
Background
Pyrethroid pesticides are a broad-spectrum insecticide widely used worldwide. Although compared with traditional pesticides such as organic chlorine, organic phosphorus and the like, the pyrethroid has the advantages of short half-life period and low toxicity. However, with the rapid development of agriculture and aquaculture, the scale of pyrethroid pesticides is also increasing, and pyrethroids exposed to the environment are prone to cause chronic toxic effects in humans and animals. In addition, the pyrethroid content in the water environment is continuously increased through the approaches of dry and wet sedimentation in the atmosphere, rainfall runoff, direct application, pesticide production factory discharge and the like. The pyrethroid has higher toxicological activity on aquatic organisms, and a large amount of pyrethroid in the water environment can influence the quality of the water environment, endanger the ecological system of the water body and cause the quality reduction of the aquatic products. In addition, by feeding, pyrethroids enter mammals, including humans, at the top of the biological chain and constitute a cumulative risk, causing damage to the relevant organs and functions of the human body, such as the endocrine system, reproductive system, immune system, central nervous system, etc.
Therefore, the detection of the pyrethroid pesticide in the water body has important significance for environmental water monitoring, quality detection of drinking water, use of the pyrethroid pesticide and risk assessment. At present, the detection method of the pyrethroid pesticide mainly comprises gas chromatography and liquid chromatography. The main sample pretreatment methods include liquid-liquid extraction, soxhlet extraction, microwave-assisted extraction, supercritical fluid extraction, solid phase microextraction, accelerated solvent extraction and the like. The solid-phase microextraction technology is a sample pretreatment technology integrating sampling, extraction, concentration and sample injection, and the stable and efficient extraction head can effectively improve the sensitivity and accuracy of analysis. At present, a stable and efficient extraction head or extractor is researched and developed, and is an important way for realizing the detection of pyrethroid pesticides in water body by solid-phase microextraction.
Disclosure of Invention
The invention aims to improve a functional extraction head of solid-phase microextraction, and provides a solid-phase microextraction device with high sensitivity and high accuracy, which is used in SPME-GC/MS to realize the detection of pyrethroid pesticides in water.
In order to achieve the aim of the invention, the invention adopts an extraction head coated with crystalline porous polymer/epoxy resin composite coating to prepare a solid-phase microextraction device, then carries out sampling, extraction, concentration and sample injection, and adopts a solid-phase microextraction (SPME) technology combined with a gas chromatography-mass spectrometry (GC-MS) method to realize the detection of pyrethroid pesticides in water.
The solid phase microextraction device is a coating fiber, is formed by composite coating of crystalline porous polymer/epoxy resin, and is prepared by the following steps: one end of the stainless steel fiber substrate with hydroxylated surface is inserted into diluted epoxy resin, slowly taken out, then inserted into prepared crystalline porous polymer powder for drying, and the operation is repeated until the required coating thickness is achieved. And finally, placing the fiber in a microsyringe to obtain the SPME extractor. Before use, the mixture is aged for 1 to 5 hours at the temperature of 230 to 280 ℃.
The thickness of the coating is 10-100 mu m.
The preparation method of the crystalline porous polymer comprises the following steps: rigid polyamine and benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (molar ratio of 0.5-2:1) were thoroughly mixed, added into a pressure-resistant glass tube, and dioxane, mesitylene and acetic acid were sequentially injected. The mixture was frozen in liquid nitrogen, evacuated and nitrogen backfilled. Finally, the glass tube is sealed in a melting way under the vacuum condition, and the reaction is heated. After the reaction is finished, the solid product is cleaned and dried, and finally the target product is obtained as brown-black solid powder.
The rigid polyamine is: tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 1,3, 5-triaminobenzene, melamine, p-phenylenediamine, 5 '-diamino-2, 2' -bipyridine.
The epoxy resin comprises the following components: bisphenol a type epoxy resin, bisphenol S type epoxy resin.
The method for detecting the pyrethroid pesticide in the water body comprises the following steps:
(1) Diluting pyrethroid pesticide with water to a required concentration to obtain a standard solution;
(2) Taking a standard solution, sequentially testing the concentration from low to high, placing the standard solution in a glass extraction bottle, uniformly stirring, and sealing;
(3) Inserting a solid-phase microextraction device based on crystalline porous polymer/epoxy resin composite coating into an extraction bottle, pushing out a fiber head, putting all the fiber heads into a sample solution, and concentrating (50-80 ℃) under stirring;
(4) After enrichment, the extraction head is drawn back into the microsyringe, then the microsyringe is drawn out and immediately inserted into a gas chromatograph sample inlet, the extraction head is pushed out again, the temperature of the sample inlet is 240-280 ℃, and the desorption time is 1-10min;
(5) And (3) carrying out linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution through gas chromatography-mass spectrometry analysis to obtain a standard curve equation of each target compound.
(6) And (3) taking a water body sample containing the pyrethroid pesticide, diluting multiple times, analyzing the water body sample according to the test method of the standard working solution in the step (2-5), measuring the peak area value of the target object, and substituting the peak area value into a standard curve equation to obtain the content of various pyrethroid pesticides in the sample.
The concentration of the pyrethroid pesticide standard solution is 1, 10, 50, 100, 500, 1000 mug/L.
The volume of the standard solution in the step 2 is 5-50mL.
The chromatographic conditions are as follows: SH-Rtx-5MS capillary column (30 m.times.0.25 μm). The flow rate of carrier gas He is 1.5mL/min; the sample injection temperature is 260-280 ℃; chromatographic column temperature program: hold at 70 ℃ for 1 minute, rise to 250 ℃ at 25 ℃/min, hold for 17 minutes.
The mass spectrum conditions are as follows: the ion source temperature is 230 ℃; interface temperature; 200 ℃.
Compared with the prior art, the invention has the following advantages:
the SPME extractor used in the present invention is a coated fiber based on a novel crystalline porous polymer/epoxy composite. Firstly, the epoxy resin is favorable for forming a film on the fiber by the crystalline porous polymer, and meanwhile, the crystalline porous polymer has certain enrichment capacity for pyrethroid pesticides (shown in figure 1, cypermethrin is taken as an example), and the synergistic effect of the crystalline porous polymer and the pyrethroid pesticides enables the SPME extractor to have good extraction performance for the pyrethroid substances. Thus, the SPME extractor coated with the crystalline porous polymer/epoxy resin composite material has significant advantages in extraction efficiency over other resin materials and crystalline porous material composites, as shown in FIG. 2. Secondly, the crystalline porous polymer is a novel porous adsorbent, and the microscopic framework of the novel porous adsorbent contains a large number of N, S heterocyclic structures, has regular pore channels with adjustable sizes, has a large specific surface area and has good enrichment and adsorption capacity on pyrethrin substances. The functional extraction head which is prepared by combining the two and is suitable for solid-phase microextraction can effectively improve the SPME extraction efficiency, and the extraction efficiency can reach 1.5-150 times of various commercial SPME extractors, as shown in figure 3. Thereby remarkably improving the sensitivity of the detection of the pyrethroid substances and well realizing the qualitative and quantitative detection of the pyrethroid pesticides in the water body.
Drawings
FIG. 1 is a bar graph comparing the performance of SPME extractors for cypermethrin extraction for epoxy resin coatings and crystalline porous polymer/epoxy resin composite coatings obtained in example 1.
Fig. 2 is a bar graph comparing the extraction performance of six pyrethroid pesticides from the crystalline porous polymeric/silicone resin composite coating and crystalline porous polymeric/epoxy resin composite coating obtained in example 1.
FIG. 3 is a comparison of the performance of the crystalline porous polymer/epoxy composite coating SPME extractor obtained in example 1 versus five commercial extractors for cypermethrin extraction.
FIG. 4 is a scanning electron micrograph of the SPME extractor obtained in example 1.
Detailed Description
For a better illustration of the invention, the following examples are given:
example 1
The solid phase microextraction device is a coating fiber, is formed by composite coating of crystalline porous polymer/epoxy resin, and is prepared by the following steps: one end of the surface hydroxylated stainless steel fiber substrate is inserted into diluted epoxy resin, slowly taken out, then inserted into prepared crystalline porous polymer powder, dried for 10 minutes at 80 ℃, and the operation is repeated until the required coating thickness is achieved. Finally, the fibers were placed in a 5. Mu.L microsyringe. The SPME extractor was obtained. Before use, the mixture was aged at 250℃for 2 hours.
The thickness of the coating is 60 mu m.
The preparation method of the crystalline porous polymer comprises the following steps: tris (4-aminophenyl) amine and benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (molar ratio: 0.5-2:1) were thoroughly mixed, added to a pressure-resistant glass tube, and dioxane 0.5mL, mesitylene 0.5mL and acetic acid (6M) 750 μl mL were sequentially injected. The mixture was frozen in liquid nitrogen for 30 minutes, evacuated for 30 minutes, backfilled with nitrogen, and repeated 5 times. Finally, the glass tube is sealed under vacuum, and reacted for 5 days at 120 ℃. After the reaction was completed, the solid product was washed with N, N-dimethylformamide and tetrahydrofuran in this order 3 times. Oven dried at 100deg.C for 24 hr.
The method for detecting the pyrethroid pesticide in the water body comprises the following steps:
the cypermethrin is diluted to the required concentration by water to be used as a standard solution, wherein the concentration is 1, 10, 50 and 100 mug/L;
taking 10mL of standard solution, sequentially testing the concentration from low to high, placing the standard solution into a glass extraction bottle, uniformly stirring, and sealing;
the solid-phase microextraction device based on crystalline porous polymer/epoxy resin composite coating is inserted into an extraction bottle, a fiber head is pushed out, the fiber head is placed into a sample solution, enrichment is carried out at 80 ℃, the solid-phase microextraction device is kept for 30 minutes, and the stirring speed is 600 revolutions per minute;
after enrichment, the sample is immediately inserted into a gas chromatography sample inlet, the extraction head is pushed out again, the temperature of the sample inlet is 270 ℃, and the desorption time is 1min;
and (3) carrying out linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution through GC/MS analysis to obtain a standard curve equation of each target compound.
And (3) taking 1mL of a water body sample containing the cypermethrin pesticide, diluting to 5mL, analyzing the water body sample according to the test method, measuring the peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining that the cypermethrin content in the sample is 89.23 mug/L.
Example 2
The deltamethrin is diluted to the required concentration by water to be used as a standard solution, wherein the concentration is 1, 10, 50 and 100 mug/L;
taking 10mL of standard solution, sequentially testing the concentration from low to high, placing the standard solution into a glass extraction bottle, uniformly stirring, and sealing;
the solid-phase microextraction device based on crystalline porous polymer/epoxy resin composite coating is inserted into an extraction bottle, a fiber head is pushed out, all the fiber heads are placed into a sample solution, enrichment is carried out at 80 ℃, the solid-phase microextraction device is kept for 30 minutes, and the stirring speed is 600 revolutions per minute;
after enrichment, the extraction head is drawn back into the microsyringe, then the microsyringe is drawn out and immediately inserted into a gas chromatograph sample inlet, the extraction head is pushed out again, the temperature of the sample inlet is 270 ℃, and the desorption time is 1min;
and (3) carrying out linear regression analysis on the measured peak area (y) and the mass concentration (x) of the standard solution through GC/MS analysis to obtain a standard curve equation of each target compound.
And (3) taking 1mL of a water body sample containing deltamethrin pesticide, diluting to 5mL, analyzing the water body sample according to the test method, measuring the peak area value of a target object, substituting the peak area value into a standard curve equation, and obtaining the deltamethrin content in the sample as 102.23 mug/L.
The preparation method of the solid phase microextraction device of the crystalline porous polymer/epoxy resin composite coating comprises the following steps: one end of the surface hydroxylated stainless steel fiber substrate is inserted into diluted epoxy resin, slowly taken out, then inserted into prepared crystalline porous polymer powder, dried for 20 minutes at 60 ℃, and the operation is repeated until the required coating thickness is achieved. Finally, the fibers were placed in a 5. Mu.L microsyringe. The SPME extractor was obtained. Before use, the mixture was aged at 260℃for 5 hours.
The thickness of the coating is 100 μm.
The preparation method of the crystalline porous polymer comprises the following steps: 1,3, 5-tris (4-aminophenyl) benzene and benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde (molar ratio: 0.5-2) were thoroughly mixed, added to a pressure-resistant glass tube, and dioxane 0.5mL, mesitylene 0.5mL and acetic acid (6M) 750. Mu.L mL were sequentially injected. The mixture was frozen in liquid nitrogen for 30 minutes, evacuated for 30 minutes, backfilled with nitrogen, and repeated 5 times. Finally, the glass tube is sealed under vacuum, and reacted for 5 days at 120 ℃. After the reaction was completed, the solid product was washed with N, N-dimethylformamide and tetrahydrofuran in this order 3 times. Oven dried at 150deg.C for 12 hr.
Claims (2)
1. The application of the solid phase microextraction device made of the coated fiber in pesticide detection is characterized in that the solid phase microextraction device is used for detecting pyrethroid pesticides in water;
the solid-phase microextraction device is formed by composite coating of crystalline porous polymer and epoxy resin, and is prepared by the following method:
(1) Inserting one end of the stainless steel fiber substrate with the hydroxylated surface into diluted epoxy resin, slowly taking out, and then inserting into crystalline porous polymer powder for drying;
(2) Repeating the operation of the step (1) until the required coating thickness is reached; finally, placing the fibers in a microsyringe to obtain a solid-phase microextractor;
the crystalline porous polymer is prepared by the following method: mixing rigid polyamine and benzo [1,2-b:3,4-b ':5,6-b' ] trithiophene-2, 5, 8-trialdehyde, adding into a pressure-resistant glass tube, and sequentially injecting dioxane, mesitylene and acetic acid; freezing the mixture in liquid nitrogen, vacuumizing, and backfilling with nitrogen; finally, the glass tube is sealed in a melting way under the vacuum condition, and the reaction is heated; after the reaction is finished, cleaning and drying the solid product to finally obtain a target object;
the rigid polyamine is: tris (4-aminophenyl) amine, 1,3, 5-tris (4-aminophenyl) benzene, 1,3, 5-triaminobenzene, melamine, p-phenylenediamine, 5 '-diamino-2, 2' -bipyridine;
the epoxy resin comprises the following components: bisphenol a type epoxy resin, bisphenol S type epoxy resin.
2. The use of a solid phase microextraction device made of coated fibers according to claim 1 for pesticide detection, wherein the thickness of the coating is 10-100 μm.
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